Polymerizable acryloyloxyarylenesulfonamides

ABSTRACT

Disclosed herein are monomeric compounds having the formula: ##STR1## wherein: R and R 1  are independently hydrogen, halide or alkyl; 
     R 2  and R 3  are independently hydrogen, alkyl, cycloalkyl, aryl or aralkyl; 
     q is 0 or 1; and 
     Ar is arylene wherein no more than one of R 2  and R 3  is hydrogen, and a method of preparing same. 
     These monomers can be homopolymerized or coplymerized with one or more other monomers to yield polymers having desirable solubility characteristics. In particular, copolymerizable ethylenically unsaturated monomers can comprise aldehyde-containing vinylaryl ethers to yield crosslinkable polymers useful in relief image materials or as binders in photographic layers.

This is a division of application Ser. No. 022,406, filed Mar. 21, 1979now U.S. Pat. No. 4,289,865.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to organic materials which are useful inpreparing polymers particularly useful in the graphic arts andphotographic arts fields. In one of its aspects, it relates to the useof such materials to prepare polymers which can be incorporated intoradiation-sensitive elements to obtain a desirable combination ofproperties. In another of its aspects, it relates to the preparation ofsuch organic materials.

2. Description of the Prior Art

The formation of ethylenically unsaturated monomers by reacting an acylhalide material with a substituted phenol is known. For instance, Naitoet al, Mokuzai Gakkaishi, 22 (8), 1976, pages 461 through 465, disclosesa reaction of o-methoxyphenol with poly(methacryloyl chloride) to formpoly(o-methoxyphenyl methacrylate). U.S. Pat. No. 3,024,221, issued Mar.6, 1962, discloses the reaction of a vinyl acyl halide with a sulfonicacid substituted phenol.

U.S. Pat. No. 2,566,162, issued Aug. 28, 1961, discloses vinylsulfonilimide monomers formed by reacting a sulfonilimide with anacrylyl or methacrylyl halide in a basic environment. However, thesepolymers are not soluble in acetone, which is the preferred solvent forcoating polymeric binders for radiation-sensitive elements.

It would be highly desirable to have available vinyl ester monomers withpendant arylenesulfonamide groups which are soluble in acetone. It wouldalso be desirable to have available a method of incorporating suchpendant groups into polymers.

SUMMARY OF THE INVENTION

The present invention provides polymerizable vinyl arylenesulfonamideesters which are soluble in acetone, methyl ethyl ketone,tetrahydrofuran and dioxane, and are easily prepared from readilyavailable starting materials. The present invention also providespolymers containing pendant arylsulfonamide groups formed from suchmonomers.

The polymers of the present invention are useful in many applications,but are particularly useful as copolymers in radiation-sensitivematerials used in the graphic arts. Such copolymers which can alsocomprise units of polymerized vinyl ethers having pendant aldehydegroups can crosslinked with reagents, such as amines, to provide organicsolvent insoluble areas. These insoluble areas in light-exposed regionsof a lithographic plate or photoresist provide negative relief images.Preferred uses for the polymers of this invention are disclosed in U.S.Pat. No. 4,239,848, issued Dec. 16, 1980.

Certain other copolymers can comprise units of polymerized ethylenicallyunsaturated monomers having ionic groups which form copolymers solublein solvent systems, such as acetone-water mixtures, water, methanol,alcohol-water mixtures and the like. Such anionic or cationic copolymersare suitable for aqueous processing.

The polymers of the present invention are also useful as binder vehiclesin a variety of applications, such as in various light-sensitivecompositions, subbing layers and the like.

One aspect of the present invention comprises a compound having theformula: ##STR2## wherein:

R and R¹ are independently hydrogen, halide or alkyl;

R² and R³ are independently hydrogen, alkyl, cycloalkyl, aryl oraralkyl, but no more than one of R² and R³ can be hydrogen;

q is 0 or 1; and

Ar is arylene.

In another aspect of the present invention, a process of preparing thecompounds of formula (I) comprises reacting a compound having theformula: ##STR3## with a compound having the formula:

    HO--Ar--(CH.sub.2)q--SO.sub.2 NR.sup.2 R.sup.3

in an organic solvent medium wherein R, R¹, R², R³, q, and Ar are asdefined above, and X is a halide.

Still another aspect of the present invention comprises a polymer formedfrom: (a) about 1 to about 100 mole percent of one or more monomershaving formula (I), and (b) from 0 to about 99 mole percent of one ormore additionally ethylenically unsaturated polymerizable monomers.

In still another aspect of the present invention, a process of preparingthe above-described polymer comprises (1) reacting a vinyl acyl halidehaving the formula: ##STR4## with a hydroxy compound having the formula:

    HO--Ar--(CH.sub.2).sub.q --SO.sub.2 NR.sup.2 R.sup.3

in an organic solvent medium wherein R, R¹, R², R³, Ar, q and X are asdefined above, and (2) polymerizing the monomer formed in step (1) with0 to 99 mole percent of one or more additional ethylenically unsaturatedpolymerizable monomers.

DETAILED DESCRIPTION OF THE INVENTION

The monomers of the present invention are depicted by the formula:##STR5## wherein:

R and R¹ are independently hydrogen; halide, such as fluoride, chloride,bromide and iodide; or alkyl, preferably having from 1 to 4 carbonatoms, such as methyl, ethyl, propyl, isopropyl, tert-butyl and thelike, including substituted alkyls, such as haloalkyls, such aschloromethyl, 1,2-dibromoethyl and the like;

R² and R³ are independently hydrogen, but only one of R² and R³ can behydrogen; alkyl, preferably having from 1 to 10 carbon atoms, such asmethyl, ethyl, n-butyl, tert-butyl, hexyl, 2,3-dimethyloctyl and thelike, including substituted alkyls such as described above; cycloalkyl,preferably having 4 to 10 carbon atoms, such as cyclobutyl, cyclopentyl,cyclohexyl, 1,3-dimethylcyclooctyl and the like, and substitutedcycloalkyls having substituents such as those listed for the alkylgroups described above; or aryl, preferably having 6 to 18 carbon atoms,including phenyl, naphthyl, anthryl and aryl groups substituted withsubstituents such as alkyl, halides, nitro, alkoxy and the substituentsas described for the above alkyl groups; or aralkyl, preferably havingfrom about 7 to 20 carbon atoms, including benzyl, methylbenzyl,diphenylmethyl and chlorobenzyl;

Ar is arylene, preferably having from 6 to 18 carbon atoms, includingphenylene, naphthylene, phenylenedimethylene, diphenylene and the likewhich can be substituted or unsubstituted, for example, with alkyl,preferably containing 1 to 4 carbon atoms, halide, sulfonamido, nitro,alkoxy and the like substituted groups as described above; and

q is 0 or 1.

Exemplary monomers corresponding to formula (I) includeN-butyl-4-methacryloyloxybenzenesulfonamide,N-phenyl-4-methacryloyloxybenzenesulfonamide,N-cyclohexyl-4-acryloyloxybenzenesulfonamide,N,N-dimethyl-4-methacryloyloxy-1-naphthylenesulfonamide,4-α-chloromethacryloyloxybenzenesulfonamide and the like.

Preferred monomers of the present invention are those of formula (I)wherein R and R² are hydrogen, R¹ is hydrogen or methyl, R³ is alkyl oraryl, and Ar is phenylene. Particularly preferred monomers areN-butyl-4-methacryloyloxybenzenesulfonamide andN-methyl-4-methacryloyloxybenzenesulfonamide.

The process of preparing monomers of formula (I) comprises reacting avinyl acyl halide compound having the formula: ##STR6## with a hydroxycompound having the formula:

    HO--Ar--(CH.sub.2).sub.q --SO.sub.2 NR.sup.2 R.sup.3

in an organic solvent medium. R, R¹, R², R³, Ar, q and X are as definedabove.

Typical vinyl acyl halides include methacryloyl chloride, methacryloylbromide, acryloyl chloride, ethacryloyl chloride, α-chloroacryloylchloride and the like. It is noted that many other halides could be usedto prepare the monomers described hereinabove.

Similarly, typical hydroxy compounds useful herein include substitutedor unsubstituted N-alkyl-4-hydroxybenzenesulfonamides,hydroxynaphthylenesulfonamides, and the like. The sulfonamides can beprepared from readily available materials according to methods wellknown in the art, such as described in Wagner et al, J. Med. Chem.,8(3), 377 (1965), and U.S. Pat. No. 2,929,710.

The described reactants are reacted in the presence of an acid acceptorwhich is defined as a compound which will react with the released haloacid condensate to form a salt and aid in shifting equilibrium toproduct. Exemplary acid acceptors include hydroxides, such as alkalimetal hydroxides, alkaline earth metal hydroxides, quaternary alkylammonium hydroxides and the like; alkoxides, such as aluminum butoxide,calcium isopropoxide, sodium ethoxide and the like; carbonates, such assodium carbonate, potassium carbonate, calcium carbonate and the like;trialkylamines, such as triethylamine, tributylamine and the like;pyridine; picoline; lutidine; weak base ion-exchange resins, such asAmberlite IR4B and Amberlite IR-45 (products sold commercially by Rohmand Haas Company) and the like; and others well known in the art. Theacid acceptors are generally present in the reaction mixture in ratiosof 1:1 to 2.2:1.0 with the hydroxy compound.

Stoichiometrically, one mole of each of the reactants is required toproduce one mole of monomer and one mole of salt byproduct. Actually, itmay be desired to provide an excess of the vinyl acyl halide compound.Suitable molar ratios of the halide to the hydroxy compound can bebetween about 2:1 and about 1:1, and preferably between about 1.2:1.0and about 1.0:1.0.

If desired, a mutual inert solvent can be employed to dissolve thereactants or serve as a heat transfer medium. The use of inert solventsis particularly desirable in a continuous method of preparation. Theproducts can be removed from the reaction solvent by any suitable meanssuch as filtration, recrystallization and the like. The amount ofsolvent is not critical and can vary between about 75 and about 99weight percent of the reaction mixture, with between about 83 and about93 weight percent being preferred. Suitable solvents include chlorinatedsolvents, such as methylene chloride, ethylene chloride and the like;diethyl ether; tetrahydrofuran and the like.

The reaction generally proceeds at a temperature between about -10° and10° C., and preferably between about -5° to about 0° C. The reactionpressure can be from subatmospheric to superatmospheric pressures of1,000 psig or higher. Typically, the reaction is carried out atatmospheric pressure.

The reaction time is a function of reaction temperature, pressure andthe particular reactants employed. In general, reaction times arebetween about 0.5 and about 4 hours, but shorter times can be employedwith more active reactants and longer times for less active reactants.

Particular reaction conditions are illustrated in examples below in thepreparation of particular monomers.

The sulfonamide-containing monomers described herein are useful inmaking the acetone-soluble polymers of the present invention.

The polymers comprise about 1 to 100 mole percent of one or morepolymerized monomers of the described formula (I). Mixtures of suchmonomers can be used, if desired, in forming the polymers.

The copolymers can comprise up to 99 mole percent of recurring unitsderived from one or more additional ethylenically unsaturatedpolymerizable monomers, each containing, for example, at least one--CH═C< or CH₂ ═C< group. Exemplary monomers include, for example, vinylesters, such as vinyl acetate, vinyl butyrate and the like; vinylamides, such as acrylamide, methacrylamide, N-methacrylamide,N-isopropylacrylamide and the like; vinyl nitriles such asacrylonitrile, methacrylonitrile, 3-butenenitrile and the like; vinylketones, such as methyl vinyl ketone and the like; vinyl halides, suchas vinyl chloride, vinyl bromide, vinylidene chloride and the like;vinyl ethers, such as allyl phenyl ether, methyl vinyl ether ando-formylphenyl vinylbenzyl ether; α,β-unsaturated acids or estersthereof, such as acrylic acid, methacrylic acid, methyl acrylate, butylmethacrylate, 2-dimethylaminoethyl methacrylate, 2-ethylhexyl acrylate,2-hydroxyethyl methacrylate, m-formylphenyl methacrylate and the like;olefins and diolefins, such as ethylene, propylene, butadiene, isoprene,1,1-di-phenylethylene and the like; vinyl aromatics, such as styrene,α-methylstyrene, p-chlorostyrene and the like;4,4,9-trimethyl-8-oxo-7-oxa-4-azonia-9-decene-1-sulfonate;2-(methacryloyloxy)ethyltrimethylammonium methosulfate;N-vinylsuccinimide; N-vinylphthalimide; N-vinylpyrazolidone and thelike. Mixtures of monomers can be used, if desired.

In one preferred embodiment of the present invention, noveluncrosslinked polymers which are soluble in acetone, tetrahydrofuran andmethyl ethyl ketone and the like, are formed from:

(a) about 1 to about 99 mole percent of one or more monomers havingformula (I); and

(b) about 1 to about 99 mole percent of one or more additionalethylenically unsaturated polymerizable monomers containing pendantaldehyde groups which crosslink with reagents, such as amines.

Exemplary of such aldehyde-containing monomers include m-formylphenylmethacrylate, m-formylphenyl acrylate, acrylamidoacetaldehyde,p-(2-methacryloyloxyethoxy)benzaldehyde and the like, as described inU.S. Pat. No. 2,929,710, which is incorporated herein by reference; andmonomers having the formula (II): ##STR7## wherein:

R⁴, R⁵, R⁶ and R⁷ are independently hydrogen or alkyl having from 1 to 4carbon atoms, such as methyl, ethyl, propyl, butyl, isopropyl,tert-butyl and the like.

R⁸ is arylene having from 6 to 18 carbon atoms, such as phenylene,naphthylene, anthrylene, biphenylylene, including arylenes substitutedwith any of the above substituents;

m is an integer of from 1 to 4; and

n is an integer of from 0 to 4.

Exemplary monomers corresponding to formula (II) include o-, p- orm-formylphenyl vinylbenzyl ether; o-, p- or m-(2-formylethoxy)phenylvinylbenzyl ether; 2- , 3- or 4-formylnaphthyl vinylbenzyl ether o-, p-or m-formylbiphenylyl vinylbenzyl ether; o- or p-formyl-2-methylphenylvinylbenzyl ether and the like. Mixtures of these monomers can be used,if desired.

Preferred polymers of the present invention formed from monomers havingformula (II) are those wherein R⁴, R⁵, R⁶ and R⁷ are all hydrogen, andmost preferably when, additionally, m is 1 and n is 0. Particularlypreferred polymers are obtained when R⁸ is phenylene, including suchmonomers as o-, p- or m-formylphenyl vinylbenzyl ether.

Methods of preparing monomers of formula (II) are discussed in U.S. Pat.No. 4,225,689, issued Sept. 30, 1980.

In another embodiment, novel copolymers soluble in acetone-water,methanol, methanol-water and water solvent systems when used in minoramounts are suitable for aqueous coating and processing. Thesecopolymers can be formed from:

(a) about 1 to about 99 mole percent of one or more monomers havingformula (I); and

(b) about 1 to about 99 weight percent of one or more additionalethylenically unsaturated polymerizable monomers having ionic groups.

Exemplary copolymerizable monomers include the following and/or theirsalts:

N-(2-methacryloyloxyethyl)-N,N,N-trimethylammonium methosulfate

N-benzyl-N,N-dimethyl-N-vinylbenzylammonium chloride

Aconitic acid

2-Acrylamido-2-methylpropanesulfonic acid

3-Acrylamidopropane-1-sulfonic acid

Acrylic acid

Methacrylic acid

4-Acryloyloxybutane-1-sulfonic acid

3-Acryloyloxypropionic acid

3-Acryloyloxybutane-1-sulfonic acid

3-Acryloyloxypropane-1-sulfonic acid

4-t-Butyl-9-methyl-8-oxo-7-oxa-4-aza-9-decene-1-sulfonic acid

α-Chloroacrylic acid

Maleic acid

Chloromaleic acid

2-Methacryloyloxyethyl-1-sulfonic acid

Citraconic acid

Crotonic acid

Fumaric acid

Mesaconic acid

α-Methyleneglutaric acid

Monoethyl fumarate

Monomethyl α-methyleneglutarate

Monomethyl fumarate

Vinylsulfonic acid

p-Styrenesulfonic acid

4-Vinylbenzylsulfonic acid

Acryloyloxymethylsulfonic acid

4-Methacryloyloxybutane-1-sulfonic acid

2-Methacryloyloxyethane-1-sulfonic acid

3-Methacryloyloxypropane-1-sulfonic acid

2-Acrylamidopropane-1-sulfonic acid

2-Methacrylamido-2-methylpropane-1-sulfonic acid

3-Acrylamido-3-methylbutane-1-sulfonic acid; and

Maleic anhydride

The preferred monomer having an ionic group isN-(2-methacryloyloxy)ethyltrimethylammonium methosulfate.

Although the amount of polymerized monomer of formula (I) incorporatedin the polymers of the present invention can vary from about 1 to about100 mole percent, preferably the amount is from about 50 to about 99mole percent. The preferred amount of additional ethylenicallyunsaturated polymerizable monomers is from about 0 to about 50 molepercent.

Exemplary polymers of the present invention includepoly(N-butyl-4-methacryloyloxybenzenesulfonamide),poly(N-phenyl-4-methacryloyloxybenzenesulfonamide),poly(N-cyclohexyl-4-acryloyloxybenzenesulfonamide),poly(N,N-dimethyl-4-methacryloyloxy-1-naphthylenesulfonamide),poly(N-butyl-4-methacryloyloxybenzenesulfonamide-co-o-formylphenylvinylbenzyl ether),poly(N-phenyl-4-methacryloyloxybenzenesulfonamide-co-m-formylphenylmethacrylate) and the like.

The process of preparing the polymers of the present invention comprisestwo steps, the first being that of making sulfonamide monomers by themethod described earlier. The second step comprises homopolymerizationof these monomers or copolymerization with each other, or with theadditional ethylenically unsaturated polymerizable monomers.

Polymerization can be carried out using techniques available to thoseskilled in the polymer chemistry art, including bulk, suspension,emulsion, solution and continuous techniques. Preferably, it is carriedout in organic solvent solutions, usually solvents such as p-dioxane,N,N-dimethylformamide, tetrahydrofuran and the like, and most preferablyin p-dioxane.

The temperature at which the polymers of the present invention areprepared is subject to wide variation, since this temperature dependsupon such variable features as the specific monomers used, duration ofheating, pressure employed and like considerations. However, thepolymerization temperature generally does not exceed about 110° C., andmost often it is in the range of about 40° to about 100° C. Thepolymerization can be carried out in a suitable vehicle, for example,water or mixtures of water with water-miscible solvents, as exemplifiedby methanol, ethanol, propanol, isopropyl alcohol, butyl alcohol, andthe like when emulsion or suspension techniques are used. The pressureemployed in the polymerization, if any, is usually only sufficient tomaintain the reaction mixture in liquid form, although eithersuperatmospheric or subatmospheric pressures can be used. Theconcentration of polymerizable monomer in the polymerization mixture canbe varied widely with concentrations of up to about 80 percent byweight, and preferably from about 10 to about 50 percent by weight,based on the weight of the vehicle, being satisfactory. Suitablecatalysts for the polymerization reaction include, for example, fromabout 0.001 to about 2.0 weight percent of free radical catalysts, suchas hydrogen peroxide, cumene hydroperoxide, azo-type initiators and thelike. In redox polymerization systems, conventional ingredients can beemployed. If desired, the polymer can be isolated from the reactionvehicle by freezing, salting out, precipitation in a non-solvent, suchas diethyl ether, or any other procedure suitable for this purpose.

As indicated in U.S. Pat. No. 3,142,568, issued July 28, 1964, it issometimes advantageous to include a surface active agent or compatiblemixtures of such agents in emulsion or suspension preparation of vinylor addition polymers. Suitable wetting agents include the nonionic,ionic and amphoteric types, as exemplified by the polyoxyalkylenederivatives, amphoteric amino acid dispersing agents, includingsulfobetaines and the like. Such wetting agents are disclosed in U.S.Pat. Nos. 2,600,831, issued July 17, 1952; 2,271,622, issued Feb. 3,1942; 2,271,623, issued Feb. 3, 1942; 2,275,727, issued Mar. 10, 1942;2,787,604, issued Apr. 2, 1957; 2,816,920, issued Dec. 17, 1957; and2,739,891, issued Mar. 27, 1956.

The equivalent molecular weights of the polymers of the presentinvention are subject to wide variation, but typically can be within therange of from about 10,000 to about 500,000. These polymers generallyhave inherent viscosities within the range of from about 0.10 to about2.0, preferably from about 0.20 to about 1.4, as measured (unlessotherwise indicated in this specification) in a 1:1 (weight)phenol-chlorobenzene mixture (0.25 g polymer in 100 ml) at 25° C. Asused herein, the term "inherent viscosity" is determined by the formula:##EQU1## wherein:

η_(inh) is the inherent viscosity;

η_(rel) is the relative viscosity of a phenol-chlorobenzene solution ofthe polymer; and

C is the concentration in grams (0.25) of polymer per 100 cc ofsolution.

The polymers of the present invention typically have glass transitiontemperatures within the range of about -10° to about 200° C. Thesetemperatures can be determined by differential scanning colorimetry, asdisclosed in Techniques and Methods of Polymer Evaluation, Volume 2,Marcel Dekker, Inc., New York, 1970.

The polymers of the present invention are soluble in a variety oforganic solvents, including acetone, tetrahydrofuran,N,N-dimethylformamide, methyl ethyl ketone and the like. Typically,these solvents are used in the graphic arts to remove unexposed areas ofphotoresists or lithographic plates. Solubility is defined as for use asdeveloper solvents that the crosslinking of the polymer results in adistinct solubility differential in organic solvents such that saidsolvents will dissolve uncrosslinked polymer but not crosslinkedpolymer, and for imaging compositions such as described in U.S. Pat. No.4,239,848 as 1.9 g of polymer dissolving in 9.6 cc of acetone. Thecrosslinkable polymers become insoluble after they are crosslinked.

The polymers of the present invention are particularly useful as bindersin an imaging system comprising an aromatic dialdehyde capable ofreacting with amines to form a dye, a material capable of generatingamines in response to activating radiation and a binder that providesimproved maximum densities for such an imaging system, such as describedin U.S. Pat. No. 4,239,848.

The polymers are compatible with radiation-sensitive compositions andare thus useful as binders for these materials in coating compositions.

The polymers, in order to be useful as photographic binders inapplications described in copending U.S. Pat. No. 4,239,848, must besoluble in acetone as other solvents, such as alcohols reactdetrimentally with the phthalaldehyde and are not sufficiently volatile.The solvents remain in the coatings and increase the efficiency of dyeformation, possibly as a result of decreased matrix viscosity. Thisproduces a long-term stability problem. Although the coatings haveexcellent speeds when fresh, the speed drops upon storage as the solventcontinues to evaporate from the layers. Therefore, solvents such asdimethylformamide are too nonvolatile for use. 1,4-Dioxane is toononvolatile and toxic in addition to a tendency to form explosiveperoxides. Cellulosic materials are highly toxic, react with aldehydesand are not volatile enough. The alcohols will react with the aldehydes,especially phthalaldehyde, and therefore are not useful. Ethyl acetateand chlorinated solvents will not dissolve the resulting polymers.

This invention is further illustrated by the following examples,although it will be understood that these examples are included merelyfor purposes of illustration, and are not intended to limit the scope ofthe invention.

EXAMPLE 1 Preparation of N-Butyl-4-methacryloyloxybenzenesulfonamide

A solution of 20.91 g (0.20 mol) of methacryloyl chloride in 80 ml ofmethylene chloride was added to a solution of 45.86 g (0.20 mol) ofN-butyl-4-hydroxybenzenesulfonamide, 20.24 g (0.20 mol) of triethylamineand 320 ml of methylene chloride and cooled to 0° C. over a period ofapproximately 20 minutes. The mixture was then stirred for another 1.5hours with cooling, washed three times with water, dried over magnesiumsulfate and concentrated in vacuo in a warm water bath. The resultantoil (Note 1) was cooled and crystallized to an oily solid. Removal ofresidual solvent with high vacuum caused this material to completelysolidify. This solid was recrystallized from 600 ml of cyclohexane withfiltering. Collection of the white solid and drying at room temperaturein vacuo gave 38.9 g of N-butyl-4-methacryloyloxybenzenesulfonamide;m.p.=59° to 60° C.

(Note 1: The oil obtained at this degree of purification was found to besufficiently pure for use in polymerizations. Unless otherwiseindicated, this form of the product was employed in the polymerexamples.)

Anal. Calc. for C₁₄ H₁₉ NO₄ S: C, 56.5; H, 6.4; N, 4.7; S, 10.8. Found:C, 56.1; H, 6.5; N, 4.9, S, 10.6.

EXAMPLE 2 Preparation of N-Phenyl-4-methacryloyloxybenzenesulfonamide

A solution of 3.31 g (0.03169 mol) of methacryloyl chloride in 60 ml ofmethylene chloride was added to a solution of 7.9 g (0.03169 mol) ofN-phenyl-4-hydroxybenzenesulfonamide, 7.06 g (0.0697 mol) oftriethylamine and 60 ml of methylene chloride at -5° C. over a period of15 minutes. The reaction mixture was stirred at reduced temperature foranother 2 hours, after which the solution was washed once with 2 percenthydrochloric acid and twice with water. The solution was dried oversodium sulfate, and concentrated in vacuo with warm water bath-heating.The resultant oil crystallized on cooling. This solid was recrystallizedfrom ethanol:water (3:2), collected and dried in vacuo. The yield ofN-phenyl-4-methacryloyloxybenzenesulfonamide was 7.05 g; m.p.=101° to102° C.

Anal. Calc. for C₁₆ H₁₅ NO₄ S: C, 60.6; H, 4.8; N, 4.4; S, 10.1. Found:C, 60,7, H, 4.7; N, 4.3; S, 10.4.

EXAMPLE 3 Preparation of N-Methyl-4-methacryloyloxybenzenesulfonamide

To a solution of 15.00 g (0.08 mole) ofN-methyl-4-hydroxybenzenesulfonamide, 8.11 g (0.08 mole) oftriethylamine and 200 ml of methylene chloride cooled to 0° C. was addeda solution of 8.37 g (0.08 mole) of methacryloyl chloride in 100 ml ofmethylene chloride over a period of approximately 30 minutes. Thesolution was then stirred for another 3 hours with cooling; washed oncewith 100 ml of 2 percent HCl solution, and twice with water; dried overmagnesium sulfate and concentrated in vacuo in a warm water bath. Theresultant solid was recrystallized from 150 ml of ethyl alcohol:water(1:1) with filtering through diatomaceous earth. Collection of the whitesolid and drying at room temperature in vacuo gave 16.20 g (79.9 percentof theory) of N-methyl-4-methacryloyloxybenzenesulfonamide; m.p.=106° to107° C.

Anal. Calc. for C₁₁ H₁₃ NO₄ S: C, 51.8; H, 5.1; N, 5.5; S, 12.6. Found:C, 51.7; H, 5.5; N, 5.7; S, 12.3.

EXAMPLE 4 Polymerization of N-Butyl-4-methacryloyloxybenzenesulfonamide

A solution of 29.74 g (0.10 mol) ofN-butyl-4-methacryloyloxybenzenesulfonamide and 30 ml of dioxane waspurged with nitrogen. To this solution was added 0.074 g of2,2'-azobis(2-methylpropionitrile), and the resulting mixture was heatedin a 60° C. bath with nitrogen purge for 16 hours. The resulting highlyviscous solution was diluted to 500 ml with dioxane and added to diethylether with rapid stirring. The precipitated polymer was collected anddried at room temperature with high vacuum. The yield of polymer was29.3 g and the inherent viscosity was 0.98.

EXAMPLE 5 Polymerization of N-Phenyl-4-methacryloyloxybenzenesulfonamide

A mixture of 21.5 g of N-phenyl-4-methacryloyloxybenzenesulfonamide and48.5 g of dioxane was placed in a 125-ml vial with 0.0215 g of2,2'-azobis(2-methylpropionitrile) and sealed. The mixture was purgedwith nitrogen for 0.5 hours and then swirled in a 60° C. bath for 96hours. The resultant solution was poured into diethyl ether toprecipitate polymer which was then collected and dried in vacuo at 50°C. The yield of polymer was 14.0 g and the inherent viscosity was 0.73.The glass transition temperature was 132° C.

EXAMPLES 6 THROUGH 13 Polymerization ofN-Butyl-4-methacryloyloxybenzenesulfonamide and o-Formylphenyl VinylBenzyl Ether

A mixture of 54.7 g (0.184 mol) ofN-butyl-4-methacryloyloxybenzenesulfonamide, 44.0 g (0.184 mol) ofo-formylphenyl vinyl benzyl ether and 400 ml of dioxane was purged withnitrogen. 2,2'-Azobis(2-methylpropionitrile) (0.494 g) was added, andthe mixture was heated in a 60° C. bath with a nitrogen sweep forapproximately 20 hours. The resultant solution was added to a largevolume of diethyl ether to precipitate polymer. The resulting polymerwas isolated, rinsed again with ether and dried in a low-temperaturevacuum oven. The yield of polymer was 74.0 g and the inherent viscositywas determined to be 0.42. The glass transition temperature was 67° C.

Other copolymers made are listed in Table I, along with theirproperties.

                                      TABLE I                                     __________________________________________________________________________          Sulfonamide                                                                              Mole           Mole Polymer                                                                            T.sub.g                             Example                                                                             Monomer    Percent                                                                            Comonomer Percent                                                                            I.V. °C.                          __________________________________________________________________________    Example 7                                                                           N-butyl-4-metha-                                                                         50   o-formylphenyl                                                                          50   0.68 29                                        cryloyloxybenzene-                                                                            vinylbenzyl ether                                             sulfonamide                                                             Example 8                                                                           N-butyl-4-metha-                                                                         50   o-formylphenyl                                                                          50   1.24 85                                        cryloyloxybenzene-                                                                            vinylbenzyl ether                                             sulfonamide                                                             Example 9                                                                           N-butyl-4-metha-                                                                         67   o-formylphenyl                                                                          33   1.33 23                                        cryloyloxybenzene-                                                                            vinylbenzyl ether                                             sulfonamide                                                             Example 10                                                                          N-butyl-4-metha-                                                                         50   m-formylphenyl                                                                          50   1.34 31                                        cryloyloxybenzene-                                                                            methacrylate                                                  sulfonamide                                                             Example 11                                                                          N-butyl-4-metha-                                                                         50   m-formylphenyl                                                                          50   0.27 71                                        cryloyloxybenzene-                                                                            methacrylate                                                  sulfonamide                                                             Example 12                                                                          N-butyl-4-metha-                                                                         67   m-formylphenyl                                                                          33   1.27 19                                        cryloyloxybenzene-                                                                            methacrylate                                                  sulfonamide                                                             Example 13                                                                          N-phenyl-4-metha-                                                                        50   m-formylphenyl                                                                          50   0.10 100                                       cryloyloxybenzene-                                                                            methacrylate                                                  sulfonamide                                                             __________________________________________________________________________

Examples 11 and 13 were carried out at 20 weight percent solids based ontotal reaction solution weight and 0.5 weight percent initiator based ontotal monomer weight. Examples 7 through 10 and 12 were carried out at50 weight percent solids and 0.25 weight percent initiator.Recrystallized sulfonamide monomer was used in Example 8.

EXAMPLE 14 Polymerization ofN-Methyl-4-methacryloyloxybenzenesulfonamide

A solution of 15.00 g (0.059 mol) ofN-methyl-4-methacryloyloxybenzenesulfonamide, 60 ml ofN,N-dimethylformamide and 2,2'-azobis(2-methylpropionitrile) (0.075 g)was placed in a 125-ml vial and sealed. The vial was purged withnitrogen for one hour with hypodermic needles and swirled in a 60° C.bath for 18 hours. The resultant solution was poured into diethyl etherto precipitate polymer. The polymer was collected and redissolved inacetone and precipitated again in methylene chloride. The polymer wascollected and dried in vacuo at room temperature. The yield of polymerwas 14.50 g (96.7 percent conversion), and the inherent viscosity wasdetermined to be 0.81 dl/g.

Anal. Calc. for C₁₁ H₁₃ NO₂ S: C, 51.8; H, 5.1; N, 5.5; S, 12.6. Found:C, 51.0; H, 5.7; N, 5.8; S, 11.3.

EXAMPLE 15 Use of Polymer in Radiation-Sensitive Element

This example illustrates one use of the polymers of the presentinvention.

In 1 g of 2-methoxyethanol were dissolved 23 mg of tris(ethylenediamine)cobalt(III) heptafluorobutyrate plus 20 mg of tris(ethylenediamine)cobalt(III) trifluoromethane sulfonate. A portion (0.4 g) of thissolution was added to 3.6 g of a 10 percent solution ofpoly(N-butyl-4-methacryloyloxybenzenesulfonamide-co-m-formylphenylmethacrylate) (50:50) in acetone. Under red safelights, 8 mg of4-(2-pyridylazo) resorcinol, an amplifier, and 40 g of2-(dibenzylamino)-3-methyl-1,4-naphthoquinone, a photoactivator, wereadded. When dissolved, the resulting solution was coated with a25-micron doctor blade on a grained, anodized aluminum support. Thecoating was given an exposure of 600 ergs/cm² at a wavelength of 500 nm,heated (coating side up) for 10 seconds on a 150° C. hot block andswabbed with acetone. A negative polymer image was formed.

EXAMPLES 16 AND 17 Polymer Evaluation

Dopes were prepared according to the formula given below and were coatedat about 100 microns wet thickness and subbed poly(ethyleneterephthalate) support.

    ______________________________________                                        Phthalaldehyde            0.320   g                                           Cobalt(III)hexammine trifluoro-                                                                         0.200   g                                           acetate                                                                       2-Isopropoxy-1,4-naphthoquinone                                                                         0.0108  g                                           Surfactant                0.040   g                                           Polymeric binder          1.90    g                                           Acetone                   7.60    g                                           ______________________________________                                    

The coating block was set at 90° F. during coating and for one minutethereafter, then heated to 140° F. for five minutes for further drying.The sensitometry of the films was determined from prints preparing bycontact exposing the film for about 8 seconds through a 0.3 log E steptablet in an IBM Microcopier IID, Model 9954 exposing apparatus and thendeveloping the image by contacting the back of the film for 5 seconds toa hot block set at 140° C.

The following table lists Examples 16 and 17 evaluated along with themaximum neutral densities of the print. Control polymers A and B arethose described in U.S. Pat. No. 2,566,162, are not within the presentinvention and lack the solubility desirable for application asphotographic binders for this system. Control polymer C has thestructure: ##STR8## and also lacks the necessary solubility.

                  TABLE II                                                        ______________________________________                                        Example Polymer             D.sub.max                                                                            Solubility                                 ______________________________________                                        14      N-methyl-4-methacryloyloxy-                                                                       2.05   soluble                                            benzenesulfonamide                                                    15      N-butyl-4-methacryloyloxy-                                                                        0.65   soluble                                            benzenesulfonamide                                                    Control A                                                                             N-methyl-4-methacrylamido-                                                                        --     insoluble                                          benzenesulfonamide                                                    Control B                                                                             N-butyl-4-methacrylamido-                                                                         --     insoluble                                          benzenesulfonamide                                                    Control C                                                                             N-(4-methacrylamidophenyl)-                                                                       --     insoluble                                          methanesulfonamide                                                    ______________________________________                                    

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

What is claimed is:
 1. A compound having the formula: ##STR9## wherein:R and R¹ are independently hydrogen, halide, or alkyl having 1 to 4carbon atoms;R² and R³ are independently hydrogen, alkyl having 1 to 10carbon atoms, cycloalkyl having 4 to 10 carbon atoms, aryl having 6 to18 carbon atoms or aralkyl having 7 to 20 carbon atoms; q is 0 or 1; andAr is arylene having 6 to 18 carbon atoms wherein no more than one of R²and R³ is hydrogen.
 2. The compound of claim 1 wherein R and R² arehydrogen; R¹ is hydrogen or methyl; R³ is alkyl having 1 to 10 carbonatoms or aryl having 6 to 18 carbon atoms; and Ar is phenylene.
 3. Acompound having a formula selected from the group consisting of:##STR10##